Fibrous wax composition impervious to fluids



EIBROUS WAX COMPOSITION lMPERvIous To.

William T; Knox, In, C'ranford, and Stephen H. Dole,

Orange, N. J., assignors to Essa Research and Engineering-(Zompany, a'corporation of Delaware Application. December 2.0, 1951,. Serial No- 2.625. 40;

1i Claim. (Cl. 106-5470).

This invention relates to the production of a petroleum hydrocarbon wax composition of enhanced plastic properties suitable as a coating agent and for ot-her purposes by blending a small proportion of petrolatum or microcrystalline wax with scale wax. The invention is more particularly concerned with the production of a material impervious to fluid comprising a fibrous material coated. or impregnated with a wax composition. containing a critical amount of rnicrocrystalline wax. The present application is a continuation-in-part of U. S. Serial No. 123,801, filed October 26 1949, for William T. Knox, Jr., and Stephen H. Dole, entitled Wax Composition.

In the refining of hydrocarbon oils such as petroleum oils, it is known to segregate paraflin waxes from socalled parafiin distillates, waxylube-s.- and the like. The segregation of these Waxest is secured by a number of processes. For example, it isknown to chill the selected wax containing fraction in order to secure crystallization of the wax and to remove the wax crystals. from the oil by filtering, centrifuging and. the like. It is. also known to use. various dewaxing solvents such. as. liquid normally gaseous hydrocarbons, such as propane, as well as other solvents, such as methyl-ethyl ketone. and the like. It is also. known. to: utilize in1 dewaxing operations solvent mixtures wherein one solvent comprises a wax precipitating solvent. while the other comprises a sol uent having a high solubility for oil. A solvent ture. of this. charac er.. for. x mple, comprises 60% by volume of toluene and 40% by volume of methyl-ethyl ketone. In utilizing a mixture of} this character, it has been the practice to add the mixture in toto or- 'incrementally to the. waxy distillate. as it is beingchilled. In dewaxing; operations, it is also known to use various filter aids and other agents in order to render the dewaxing and filtering operations more efficientz,

The waxsegregated from the hydrocarbon oil, usually termed slack. wax)? contains; from about; 10% to 40% of oil'. The slack wax is refined usually by conventional sweating to produce crude scale wax, in a manner to reduce the oil content to lessthan about 5% byweight. The sl'ack wax may-be distill'ed to obtain the desiredboiling range wax prior to sweating, desired; This crude scale wax generally has an oil content of about 2% to 3% by; weight. In order to remove this oil' from the scale; wax toprod'uce a refined waxhaving an oil content below about .5%, usually" below about 3%, various procedures; have been proposed and e mployed; V

It is. also known in the art to: segregate microcrystalgline waxes from residual oils. These microcrysta lliine waxes are of a relatively high melting point and: of different crystalline structure; The microcrystalline. or petrolatum waxes may be prepared firom. any of the parafiin or mixed base crude. oils. The undistilled residue may be treated with sulfuric acid and neutralized to remove the tarry matter and unsaturated, hydrocar- The wax may be again put in solution with more sol-'- vent' or naphtha and chilled and filtered or 'recentrifuged to further reduce the oil content. The wax which separates in either of these operations is referred to as crude petrolatum wax. The wax separated in the sec.- ond deoiling process after stripping to. remove solvent is fairly dryandof a low oil content. This wax should not be confused: withpetroleumjellies which contain large amounts of oil. The crude petrolatum wax may be again put into solution with naphtha and filtered. through clay or an equivalent material in order to improve. its color; The. clay filteredvsolution is distilled to. remove the naphtha, theresidue being a refined petrolatum wax having a melting point within the range of about to 180 F. The source. of the crude oil and the oil content of the refined. microcrystalline product will affect the melting point of the. final wax. product. The refined petrolaturn wax, sometimes; called amorphous. wax, iswof very small: crystal structure.

The heneinbefore mentioned? crude. petrolatumwax may be fractionated; into petrolaturn waxes. having melting points Within! the range of 140 F. to 180 F. Usually this separationyis; effected by fractional precipitationfrom ketone, propane or naphtha solutions. The terms.pettolatumwaxesf or microcrystal-l i-ne waxes. are used in this application to cover the residual type petroleum waxes. of very Small crystalline structure, and having; melting points. abovezabout F. and. oil contents in the range of. about 1. to 10%.

Paraff n type. waxes. have; been extensively used in the coating; art,-particularly whereliquid proofness and moisture proofnesshave. been desired. Howevenparaifin wax; while inexpensive, has certain disadvantages. During sweating the, soft waxes usually considered to be isopauaflins or naphthenic compounds are dissolved out the sweatedoil, and. are thus lost: from. the. refined wax. For certain uses; in the coating field, suchas in the liquid proofing of milk cartons, the. presence. of these soft waxes is; desirable as. they exert a plasticizing effect an p event, the.-

frorn crackingf Scale wax still nt ins an appreciabl q antity of thesev soft waxes but. too. unc uous in nat re: to. be pref rr d as. o t.- ing material and possesses a mottledappearance.

Flexibility and impact strength are very mpor mdexe to. the..s11 i.tabi1.itv of. Wax s as coating, an unegue g materials. High. fl ibility has, been found o be. related. to good-p rformance. of waxes. as coating materials. atlpw temperatures. High impact strength, i... a. h gh resistance to. deformation or cracking on. imr pact, is. related to, the abilityof they wax. to, withstand rough handling and chipping,

It has now. been discovered that the, flexibilityand-imp ct. strength o f. sc:a1e w x ceatirgs can. begre lv in.- .creased by blending, with. h se. scale waxes. small amounts of. mt ro rvstallme. It, is. pre rred. hat th scale waxes. contain. more. han. about 1% 011, preferably from abo 2.19 4%. otoil... The. m erecry alline wax is. a ed In. amounts. froutl ,o,to' .Q%,.pn' .rab1v trom. about 7. o. 12%.. based on. he, etalw x composi i n.- The crude. scale-mi roeryst llin bl ndslrave a. fine. uni;- f orm. extur when solidified and are not. unctuous. As pointed out, a particularly desirable concentration of mi roc y all-i ewax to be u liz iua cor anee. with the pr sent nven io i n t e ange of. about 0 Alse. as. entioned he eto e, h in ention is pecific y coneern iw th. t pr uc ion of a flui impervio s material comprising a fibrous material, particularly paper, in conjunction. with scale wax and a critical amount of microcrystalline wax.

' The present nvent on will be more fully appreciated by reference to, the drawing: illustrating one embodiment in the temperature of the waxy distillate is progressively reduced. A typical operation is to introduce the feed oil into an initial chilling stage at a temperature of about 130 F.; to introduce the feed oil into the second chilling stage at a temperature of about 90 F.; to introduce the feed oil to the third chilling stage at a temperature of about 60 F.; to introduce the feed oil to the fourth chilling stage at a temperature of about 25 F. and to chill the same in the fourth chilling stage to a temperature in the range from about to +10 F. The operation of the respective chilling stages may be varied appreciably and either direct or indirect chilling means utilized. For purposes of illustration, it is assumed that a solvent mixture is used and that the wax-precipitant comprises methyl-ethyl ketone and that the aromatic solvent having a high solubility for oil comprises toluene. It is also assumed that 3 to 4 volumes of total solvent mixture is utilized per volume of waxy oil being dewaxed. The solvent mixture comprises 75% by volume of methylethyl ketone and 25% by volume of toluene.

The entire mixture comprising oily constituents, crystallized wax constituents, toluene and methylethyl ketone, after chilling is held at the filtering temperature and passed to filtering zone 8 wherein the solid wax particles are segregated from the oily constituents by any suitable filtering or separation means. The filtering zone may comprise drum filters, plate and frame presses, centrifuges or suitable equivalent equipment for the separation of the precipitated waxy constituents from the oily constituents. The oil and a portion of the solvent is removed from zone 8 by-means of line 9 and the wax cake washed with a wash solvent introduced into filtering zone 8 by means of line 10. Slack wax and solvent are removed from zone 8 by means of line 11 and passed to a distillation zone 12 wherein a separation is made between the wax and the solvent. It is to be understood that other means of separating the solvent from the wax may be utilized if desirable.

The wax substantially free of solvent is removed from separation zone 12 by means of line 13. The solvent mixture comprising methyl-ethyl ketone and toluene is removed overhead from zone 12 by means of line 14 and preferably recycled to the system. The oil-solvent mixture removed from filtering zone 8 by means of line 9 is introduced into a distillation zone wherein a separation is made between the oily constituents and the solvent mixture.

While the drawing illustrates a solvent dewaxing operation with respect to the production of the slack wax, it is to be understood that the waxy constituents may also be separated in a conventional plate-and-frame pressing operation- The slack wax may be then further refined to crude scale wax in zone 15, which comprises a conventional sweating operation, or solvent deoiling operation, or the like. The oil removed from zone 15 by means of line 36 may preferably be recycled to zone 7. The scale wax is removed from zone 15 by means of line 35 and may be further refined by treatment with sulfuric acid or fullers earth, bauxite or other absorbent materials, or by hydrogenation under mild treating conditions.

The residue is removed from distillation zone 1 by means of line 6 and passed into a deasphalting zone 16, wherein the asphaltic constituents are precipitated out using a deasphalting solvent, preferably propane which is introduced by means of line 50. The asphaltic constituents are removed by means of line 17, while the deasphalted oil and propane are removed by means of line 18 and passed to chilling zone 19 which may comprise a plurality of chilling zones. Additional propane may be introduced if needed by means of line 20. The chilled mass is passed to filtering zone 21 by means of line 22 wherein a separation is made between the oily constituents and the precipitated wax particles. A solvent-oil stream is removed by means of line 23 while the wax constituents are removed by means of line 24. While these waxy constituents may be utilized as such, it is preferred in order to reduce the concentration of the oil to add additional solvent such as propane by means of line 25 and to re-chill the mass in chilling zone 26. The solvent is removed from the precipitated wax particles in filter zone 27 and withdrawn by means of line 28. The waxy constituents are introduced to distillation or equivalent zone 29, wherein the remaining portions of the solvent are separated from the mircocrystalline wax. The solvent is removed by means of line 30 while the oilfree, solvent-free, microcrystalline wax is removed by means of line 31.

In accordance with the broad concept of the present invention, an improved wax composition having enhanced plastic properties is secured by the blending of the scale wax with the microcrystalline wax, is illustrated by a product removed by means of line 32. Also, in accordance with the specific concept of the present invention, this blend of microcrystalline and scale wax is heated in zone 33 and combined with a fibrous material introduced by means of line 34 to secure a fluid impervious shock resisting coated material.

While the drawing illustrates a sweating operation with respect to the production of the scale wax, it is to be understood that the waxy constituents segregated in zone 12 may be solvent deoiled in order to produce a satisfactory scale wax having an oil content below about 4%, perferably in the range from about 1% to 2.5% by weight.

The present invention may be more fully appreciated by the following examples illustrating the same:

EXAMPLE I A number of wax blends were prepared comprising various percentages of microcrystalline wax. Various tests were conducted on these blends with the following results:

TABLE I 011 hl/loduf- M. 1 Flexi- Impact F., g," Color {35; bun strength, ASTM Pep lbs/L 0.001 ft.1bs.

cent in.

131 F. ASTM Refined Wax 131 0. 5 +30 S 300 35 0. 03 +5% Petrolatum A. 131 0. 9 18 TR 530 70 0.05 +12%Petro1atum A: 132 1. 4 14 TR 650 75 0.02 +5% Petrolatum B. 131 0.6 +4 S 720 75 0.02 +5% Petrolatum O. 131 0.8 18 TR 630 70 0.01 124 F. ASTM White Scale Wax 124 2. 2 +25 S 170 45 0.10 +5% Petrolatum A. 124 2. 4 19 TR 450 0. 46 +15% Petrolatum A. 3. 1 15 TR 640 0. 50 +5% Petrolatum B- 124 1. 9 +3 8 590 100 0.65 +5% Petrolatum O- 124 2. 2 18 TR 470 95 0. 64

l S: Saybolt color; TR: Tag-Robinson color. 1 Tests conducted at 40 F.

From the above it is apparent that the addition of the microcrystalline wax improved the properties of the scale wax.

Also, the scale-microcrystalline wax blends had a much higher resistance to impact and were more flexible than the paraffin-microcrystalline wax blends, or than the crude scale wax alone. Both of these properties are highly desirable in waxes used for coating packages of paperboard, particularly for packages stored under refrigeration, such as milk cartons or frozen food packages. Whereas the addition of microcrystalline wax to refined paraffin in most cases reduced resistance to impact or increased it only slightly, if at all, the addition of microcrystalline wax to scale wax invariably increased resistance to impact. The modulus of rupture of the scalemicro blends, while not so high as that of equivalent paraffin blends, was still sufiiciently high to insure excellent performance for package coating. Although flexibility of refined wax is increased a small amount by the addition of microcrystalline, the flexibility of scale wax is increased much more.

EXAMPLE II The efiectiveness of the wax blend of the present invention as a milk carton coating composition in comparison with a typical commercial coating wax and a refined wax with the addition of microcrystalline wax is shown by the following data. These results were obtained on typical commerical milk cartons coated on a commercial machine with the experimental waxes. Coating temperatures were varied within about 20 F. to give approximately equal wax consumption values, since the amount of wax coating on a carton is known to affect the percentage leakers.

amass Cartons are filled with water (colored with methylene blue dye) stored at 40 F. for 16 hours, then dropped, in a standard manner, on one corner. Cartons are then stored for 524 hours and number or leaking cartons counted. Result expressed asnumber of leakers outof 100 cartons tested.

The cartons coated with the scalegpetrolatum :ble'n'ds showed greatly improved durability (lower ,lpercent leakers) as compared with cartons coated with a-commercial blended milk carton wax .and with a refined 'wax-petrolatum blend. Only 25 to 50% of thesecartonsdeveloped leaks in the durability testtas 'compared with .about 7.0% leakers for the other products. --Qther propertiesof the cartons, such as resistance to liquid penetration, appearance, and r gidity, WhJCh areimportant to most users, were at least as good, orbetter, with 'the scale Wax-microwax blends.

EXAMPLE III Th increased flexib l ty and impact 'strength :of 'scale wax-microcrystalline wax blends as compared with refined wax-microcrystalline wax blends cannot be attributed solely to the higher oil content of the former, since the addition of oil to a refined :wax-microcrystalline wax blend doesnot result in the:sarnejproperties'exhibited by Zthe :scalc wax-microcrystalline wax blend. This is shown in the table below:

, cogled to f F in a'cold'room for l6 hours. strips are broken "by placing them horizontally across two "6 into strips which are .pla'cedionaismooth brassjlajte Land The'wax parallel inch rods, 'and loading 'byrunning water into a bucket suspended from the center of the wax strip. The total welghtrrequired to break each strip is measured in "grams. z'I-he average of six determinations, 3 air- :cooled side 'up 'and i3 water-cooled side up, is reported 'as modulus of rupture, and calculated from the following formula:

o :gramsX-0I00463 40 width.Xthickness Paraffin flexibility .test

This test measures the distance in thousandths mt an inch through-which a-wax strip, '01'070"='thick-rnay*be*bent before breaking when displaced transversely at "a distance of one inch'from the secured end. 'Thetestis carried out .at 40 1E. Two wax .di'scs, one 'eiboutTOE'OS" thick and one about 0.09" thick, are ,prepared in =-a similar .manner it'o. the discs prepared in the Modulus of :rupture" rtest and similarly cut into 6 strips, e'a'ch 3"by .5". iAwaxstrip is broken by holding one end firmly in a vise in a ver- :tical .position and displacing the strip with a micrometer at a distance of one inch from the vise "jaws "until "the first sign 0f a crack :appears in the (strip. :Micrometer extension .is recorded and thickness of each specimen measured.

"samples are' brokemfor each.thickuess, 13 abrokenaircooled side ,facing .micrometer and 3 water-cooled side facing the micrometer. Displacement 'for 'a-0.'070"thick specimen is obtained by interpolation (log+log plot) between .the .average displacement .of the 0.05" and the 0.09" specimen. This interpolated value, expressed in thousandths of an inch, is reported as flexibility.

TABLE .III

Modulus Impact are or arse P AS'TM Perentlbs/sq. m. o it.-lbs., at

at 40 F. 40 F.

Scale Wax-Microcrystalline Wax Blend (White Scale +5% Petrolatum) 124 1. 9 590 100 0. Refined Wax-Microcrystalline Wax Blend (Refined Wax +5% Petrolaturn) 131 0. 6 590 65 0.01 1. a t2 a 3-8;

0 e Scale alone (used in above en 124 2. 2 170 45 0. 10 Refined wax (used in above blend) 131 0. 5 300 35 0. 03 Lower melting point Refined Wax alone 122 0. 1 600 35 0. 25

It is evident from the above data that the flexibility and impact strength of scale wax-microcrystalline wax blends are greatly superior to refined wax-microcrystalline Waxoil blends. Even when as much as 2% oil is added, these properties are only very little improved. It is also evident from the above data that the improved properties of scale-microcrystalline wax blends is not due to the lower melting point of the scale wax. The greatly improved properties are apparently due to the fact that scale waxes contain desirable constituents which provide these very desirable properties of a coating wax and which properties are not found to such a high degree in refined wax.

In the above tables, the terms Modulus of rupture, Flexibility, and Impact strength, were determined in the following manner:

Modulus of rupture test This test is adapted to measure the stress required to break a bar of wax 0.15 thick and 0.50" wide when a load is applied at the center of a span 1.4 wide. The test is carried out at 40 F. Wax discs, 0.15" thick, are cast by pouring a Weighed sample of wax on the surface of boiling distilled water in a crystallizing dish and allowed to cool for 2. to 3 hours. These discs are then cut Impact strength test This test measures the force in foot-pounds required to crack a test specimen 0.05 to 0.06 inch thick and is carried out at 40 F. by dropping hammers of known weights on the test specimen. Two wax discs, each 0.05" to 0.06" thick prepared as in the above tests are cut into squares 1 /2" on a side and placed on a smooth brass plate and cooled to 40 F. for 16 hours. The samples are removed and held under water at 40 F. 1- 1 F. for one-half hour. Hammers are dropped on a contact rod placed on the wax specimens (air-side up) which are supported on a smooth steel plate. One determination per specimen is made until the lowest height at which cracking occurs consistently is bracketed. The product of this height times weight of hammer is reported as im pact strength.

EXAMPLE IV Additional tests were conducted to determine criticality of the amount of the microcrystalline wax used in conjunction with the scale wax and to further show the difierence between scale wax-microcrystalline Wax blends 7 and paraflin wax-microcrystalline wax blends. The results of these tests are as follows:

of oil and about 10% of microcrystalline wax having a melting point between 145 F. and 180 F.

DAIRY WAX EVALUATION 130 M. P Paraf- 124 M. P. White Scale Wax Plus- Commercial fin wax Plus Wax Blended (Ming 5% 10% Micro Micro Micro Micro Micro Micro Micro Wax Consumption, lbs /1 000 cartons 32-35 32-35 32-35 32-35 32-35 32-35 32-35 32-35 Coating temp, F 187 181 200 210 220 226 190 205 Percent leakers 71 50 19 28 30 28 52 32 40 F. Storage? Acid absorption, lbs./1,000 cartons 8. 5 7. 0 6. 0 6. 0 8. 5 11. 0 7. 0 8. 0 Bulge, Hi2 in 2 2% 2 2 3 5% 2% 2% 73 F. Storage:

Acid absorption, lbs./1,000 cartons 16. 5 12. 5 7. 5 14. 5 12. 0 12. 0 9 9 Bulge, $62 in 4 4 8 8% 9 4 5 l Cartons are filled with water (colored with methylene blue dye) stored a Cartons are then stored for 24 hours and the num ard manner on one corner. expressed as number of leakers out of 100 cartons tested,

t 40 F. for 16 hours, then dropped, in a standber of leaking cartons counted. The result is I Cartons are filled with a 1% solution of lactic acid in water (colored with methylene blue dye) then stored for 72 hours. 10 cartons stored. at 40 F. and 10 cartons stored at 73 F. After storage the weight of fluid absorbed and the increase in bulge is determined.

It is evident from these data that there is a critical amount of microcrystalline wax which, when blended with the scale wax, gives best results, both from a durability and appearance standpoint. It is also evident that the scale wax-microcrystalline wax blends are superior, when considering all desirable properties, than the paraflin wax blends containing equivalent amounts of microcrystalline wax.

What is claimed is:

An improved two-component film-forming wax composition for coating paperboard or the like, consisting essentially of scale wax containing from about 1% to 4% References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Commercial Waxes, Bennett, Chemical Publishing Co. Inc., Brooklyn, New York, 1944, pages 56 and 295. Y V\;{art1lg2;The Chemistry & Technology of Waxes, New 

